Triglycerol alkylcarbamates, their preparation and their use as emulsifying agents in cosmetic compositions in the form of wax microdispersions

ABSTRACT

A compound of the formula: 
     
         R--NHCOOCH(CH.sub.2 OCH.sub.2 CHOHCH.sub.2 OH).sub.2       (I) 
    
     wherein R is a C 10  -C 20  alkyl, optionally unsaturated, is employed in the preparation of wax microdispersions useful particularly in cosmetic composition for the hair.

This is a division of application Ser. No. 07/974,171, filed Nov. 10,1992, now U.S. Pat. No. 5,371,252, which is a Continuation ofapplication Ser. No. 07/589,651, filed Sep. 28, 1990, now abandoned.

The present invention relates to new esters of polyols, to theirpreparation and to their use, principally, as surfactant agents.

French patent No. 84.11687 (2.549.826) describes monoethers of fattyalcohols and triglycerol, useful principally as emulsifying agents incosmetic compositions, and their preparation, in the form of welldefined compounds, from the bisisopropylidene derivative of lineartriglycerol.

It has now been discovered that certain triglycerol alkylcarbamatesexhibit interesting surfactant properties, which permit their use,principally, in the preparation of cosmetic compositions.

Moreover, it is known that it is possible to obtain indefinitely, withcertain waxes, stable and water dilutable microspheres, withoutaggregation or sedimentation of the particles in suspension. Themicrodispersions of waxes are obtained by melting the wax in thepresence of a surfactant and, depending on circumstances, a portion ofwater, then progressively adding hot water with stirring. Theintermediate formation of a water-in-oil type emulsion is observedfollowed by a phase inversion with the final production of anoil-in-water type emulsion. On cooling, a stable microdispersion ofsolid colloidal wax particles is obtained; see for example,"Microemulsions Theory and Practice", L. M. Prince Ed., Academic Press(1977), pages 21-32.

Research carried out by the applicants has shown that the monoethers oftriglycerol disclosed in the above-mentioned French patent do not permitthe production of a wax microdispersion.

On the other hand, it has been found that the triglycerolalkylcarbamates of the present invention do permit the production of waxmicrodispersions.

Such wax microdispersion are useful principally as supports for cosmeticcomposition for the hair. This use in the subject of Luxembourg patentapplication No. 87.457 filed on Feb. 24, 1989 and entitled: "Use ascosmetic composition for the hair, a wax microdispersion, and processfor the treatment of hair with such a composition".

It has also been discovered that the triglycerol alkylcarbamatesexhibit, relative to the ethers of the aforementioned French patent,improved cutaneous tolerance.

The present invention thus relates to alkylcarbamates having thefollowing formula:

    R--NHCOOCH(CH.sub.2 OCH.sub.2 CHOHCH.sub.2 OH).sub.2       (I)

wherein

R represents alkyl, optionally unsaturated, having 10-20 carbon atoms.

In the compounds of formula I, the R group can represent principallyn-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl,n-octadecenyl (oleyl), 2-hexyldecyl, 2-octyldodecyl, 2-heptylundecyl,etc.

The present invention also relates to a process for preparing thecompounds of formula I.

This process comprises reacting a compound of the formula:

    R.sub.1 CH.sub.2 CH(R.sub.2)CH.sub.2 OCH.sub.2 CH(OH)CH.sub.2 OCH.sub.2 CH(R.sub.2)CH.sub.2 R.sub.1                               (II)

wherein R₁ and R₂, taken together, form a divalent group of the formula:--O--CR₃ (R₄)--O--,

R₃ and R₄, each independently, represent lower alkyl, and

wherein

the hydroxyl group of the compound of formula II is active in the formof imidazolide or chloroformate, with an amine, RNH₂, wherein R isdefined above, so as to obtain a compound having the formula:

    R.sub.1 CH.sub.2 CH(R.sub.2)CH.sub.2 OCH.sub.2 CH(OR.sub.5)CH.sub.2 OCH.sub.2 CH(R.sub.2)CH.sub.2 R.sub.1                     (III)

wherein R₅ represents --CO--NHR₁ and then hydrolyzing said compound IIIso as to obtain the corresponding compound having formula I.

Activated compound II has formula IIA:

    R.sub.1 CH.sub.2 CH(R.sub.2)CH.sub.2 OCH.sub.2 CH(OR.sub.6)CH.sub.2 OCH.sub.2 CH(R.sub.2)CH.sub.2 R.sub.1                     (IIA)

wherein R₆ represents ##STR1## or --CO--cl.

The IIA compound (imidazolide) can be obtained by reacting compound II(non-activated) with carbonyldiimidazole.

The reaction of carbonyldiimidazole and the compound of formula II iscarried out by dissolving these reactants in a solvent such astetrahydrofuran or dichloromethane. The resulting solution is stirredfor a few hours at a temperature between 20° C. and the boilingtemperature of the solvent. The resulting imidazolide of formula III canbe used directly for subsequent reactions.

Starting with compound II, it is also possible to prepare, in accordancewith known methods, the corresponding chloroformate, of formula IIAwherein R₆ is --COCl.

For reaction with the amine, the compound of formula IIA is dissolved ina solvent such as dichloromethane. The amine, RNH₂, is then added in theform of a solution, for example, in dichloromethane. In the case wherecompound IIA is a chloroformate, the reaction is carried out in thepresence of an HCl acceptor, such as pyridine or triethylamine. Thereaction medium is stirred at a temperature between, for example, 20° C.and the boiling temperature of the solvent, for several hours. Theorganic phase is then washed several times with water and dried, forexample, on sodium sulfate. The solvent is removed by evaporation underreduced pressure. The resulting compound of formula III can be submitteddirectly to hydrolysis.

Hydrolysis is carried out, for example, in a solvent such as methanol,ethanol or tetrahydrofuran in the presence of a small amount of waterand a protonated acid.

There can be employed mineral acids such as sulfuric acid, phosphoricacid or hydrochloric acid, or organic acids such as paratoluene sulfonicacid. Preferably hydrochloric acid is used.

The amount of acid can vary, for example, from 0.05 to 0.2 mole, andpreferably from 0.05 to 0.1 mole, of acid relative to the number ofmoles of the compound of formula III.

The initial reactants employed in the process of the present inventionare known or can be prepared in a known manner. The diisopropylidenetriglycerol (formula II wherein R₃ =R₄ =methyl) is a commercial productsold by Solvay.

The present invention also relates to the use of the compounds offormula I as surfactants, and principally as emulsifying agents, incosmetic compositions or in supports for cosmetic compositions. Aparticularly interesting use of the compounds of formula I is asdispersing agents in the preparation of aqueous wax microdispersions.

This use is principally characterized by the fact that the wax and atleast one compound of formula I are heated to a temperature greater thanthe melting temperature of the wax, but not greater than 100° C.,optionally in the presence of a part of water, until complete melting ofthe wax. Water, or the remainder of the water, is progressively added,the water being at a temperature at least equal to the said temperatureat which the wax is being heated. The mixture is then stirred until awax microdispersion in a continuous aqueous phase is formed. Theresulting wax microdispersion is then cooled to ambient temperature.

The present invention also relates to wax microdispersions which can beobtained by the above described process.

Representative useful waxes include, principally, waxes or mixtures ofwaxes having a final melting point greater than 60° C. but lower than100° C.

The emulsifying agent comprises at least one compound of formula I,optionally in admixture with other nonionic or anionic emulsifyingagents.

The microdispersion can contain, for example, from 0.1 to 40 percent byweight of wax and from 0.01 to 25 percent by weight of emulsifyingagent.

Preferably, the wax/emulsifying agent weight ratio varies from 1 to 30.

Generally, the wax microdispersion contains at least 35 percent ofwater.

In the resulting wax microdispersion, the size of the wax particles islower than 500 nm.

Representative useful waxes include, for example, Carnauba wax,Candelilla wax, Alfa wax and mixtures thereof.

The cited waxes or mixture thereof can also be employed in combinationwith another wax or a mixture of other waxes, for example with aparaffin wax; the weight amount of Carnauba wax and/or Candelilla wax,in such mixtures, is preferably greater than or equal to 50%.

The surfactants which can be employed in admixture with the compounds offormula I are, for example, anionic surfactants having, for example, alipophile-hydrophile balance (HLB) ranging form 10 to 40. They are,principally, salts of fatty acids (for example, alkaline salts ororganic salts such as salts of amines), the said fatty acids having, forexample, 12 to 18 carbon atoms and being able to have a double bond asin the case of oleic acid; the alkaline salts or salts of organic basesof alkyl-sulfuric and alkyl-sulfonic acids having 12-18 carbon atoms, ofalkyl-arylsulfonic acids whose alkyl chain contains from 6 to 16 carbonatoms, the aryl moiety being, for example, a phenyl group. They are alsoether-sulfates, in particular the products of sulfating fatty alcoholsand polyalkoylated alkylphenols, in which the aliphatic chain has from 6to 20 carbon atoms and the polyalkoxylated chain has from 1 to 30oxyalkylene units, in particular oxyethylene, oxypropylene oroxybutylene units.

The nonionic surfactants which can be employed in admixture with thecompounds of formula I are, principally, fatty acids or amides ofpolyalkoxylated and/or polyglycerolated fatty acids; esters of fattyacids and polyalkoxylated and/or polyglycerolated polyols fatty alcoholsor polyalkoxylated and/or polyglycerolated alkylphenols alkanediols or1,2- or 1,3-alkenediols, polyalkoxylated and/or polyglycerolated; andalkylethers of alkanediols or 1,2- or 1,3-alkenediols, polyalkoxylatedand/or polyglycerolated. The fatty acids or alcohols, optionallyunsaturated, have for example, 12 to 24 carbon atoms. The alkyl chain ofthe alkylphenols has, for example, 6 to 16 carbon atoms, the alkanediolsor alkenediols have from 9 to 24 carbon atoms, the alkyl of thealkylethers has from 4 to 20 carbon atoms, and the number of oxyalkyleneunits or (--CH₂ CHOH--CH₂ O) units can range from 2 to 40.

The polyalkoxylated nonionic derivatives are principallypolyoxyethylenated derivatives, optionally polyoxypropylenated.

The polyalkoxylated fatty acids are commercial products, and principallyproducts sold under the trade name "Myrj" by ICI Americas.

The esters of fatty acids and polyoxyethylenated polyols for which thepolyol is sorbitol are know products sold under the trade name "TWEEN"by ICI Americas.

The polyoxyethylenated fatty alcohols are commercial products, andprincipally those sold under the trade name "Brij" by ICI Americas.

The polyglycerolated fatty alcohols or polyglycerolated alkanediols oralkenediols, or alkylethers of polyglycerolated alkanediols oralkenediols can be prepared, for example, in accordance with theprocedures described in French patents 1.477.048, 2.025.681, 2.091.516and 2.465.780 or in accordance with analogous methods.

The fatty acids or amides of polyglycerolated fatty acids areprincipally described in French patent 1.484.723 or are again commercialproducts such as those sold under the trade name "Plurol" by Gattefosseor "Drewpol" by the Stefan Company.

The present invention also relates to cosmetic compositions andprincipally cosmetic composition for the hair, characterized by the factthat they contain as a surfactant or emulsifying agent, at least onecompounds of formula I.

The compositions of the present invention can contain, however, allconventional active adjuvants, vehicles and secondary components thatare desired to be included in the compositions.

The cosmetic compositions of the present invention can be providedprincipally in the form of stable wax microdispersions which have beendescribed above. These compositions in the form of wax microdispersionsare useful principally as hair styling lotions and also lotions intendedto improve the appearance of hair of persons having oily hair, as isdescribed in the Luxembourg patent application cited above.

These compositions in the form of microdispersions can contain one ormore conventional secondary adjuvants such as thickening agents,stabilizers, perfumes or preservatives.

These secondary adjuvants are added according to the situation eitherwith the initial reactants (prior to preparing the microdispersion) orin the final composition.

The nonvolatile hydrosoluble adjuvants can be added optionally in thewater employed to produce the microdispersion.

The liposoluble adjuvants are generally added to the wax before theproduction of the microdispersion.

These compositions can be applied to dry or wet hair, for example,before or after a shampoo. They can be rinsed or non-rinsed and can beapplied daily.

When they are applied before or after a shampoo, the application beingfollowed or not with a water rinse, they discipline or control the hairand impart hold and volume to the styling. In addition, they delay ahair re-oiling phenomenon which is observed with persons having oilyhair.

These compositions have a pH which can vary from 3 to 10. The pHoptionally can be adjusted using a conventional pH modifying agent.

The following non-limiting examples illustrate the present invention.

EXAMPLE 1 Compound of formula I wherein R=hexadecyl

(a) Preparation of the imidazolide

102 g (0.63M) of carbonyldiimidazole are dissolved in 500 cm³dichloromethane. To this solution there are added 500 cm³ ofdichloromethane containing 200 g (0.62M) of diisopropylidenetriglycerol, sold by Solvay. The reaction medium is stirred for 5 hoursat ambient temperature and then washed four times with 150 cm³ of water.The reaction medium is then dried on sodium sulfate and the solvent isevaporated under reduced pressure. 241 g of a compound in the form of anoil are obtained, the purity of which is sufficient for direct use inthe following reactions.

(b) Reaction with hexadecylamine

14.1 g (0.034M) of the imidazolide prepared above are dissolved in 50cm³ of dichloromethane. To this solution 7.2 g (0.03M) of hexadecylaminedissolved in 25 cm³ of dichloromethane are added. The reaction medium isthen stirred overnight at ambient temperature. It is then washed severaltimes with water. After drying the organic phase on sodium sulfate,followed by evaporation of the solvent under reduced pressure, 20 g of awaxy compound are recovered.

(c) Hydrolysis

20 g of the waxy compound obtained above are dissolved in 100 cm³ ofmethanol to which 2 cm³ of 5N HCl have been added. The reaction mixtureis stirred overnight. After filtering some slight insolubles, thesolvent is removed under reduced pressure. 17 g of a wax are obtainedand recrystallized in a 200:30 mixture of heptane and ethyl acetate. 13g of a white wax having a Kraft point at 0.5% of 21°-24° C. and a cloudpoint >100° C. are recovered. This product responds to formula I whereinR is hexadecyl.

The NMR ¹ H and ¹³ C spectra are in accord with the structure indicated.

    ______________________________________                                        Elemental analysis                                                                        Calculated                                                                            Found                                                     ______________________________________                                        C%            61.51     61.2                                                  H%            10.52     10.23                                                 N%            2.76      2.63                                                  ______________________________________                                    

EXAMPLE 2 Compound of formula I wherein R is dodecyl

To 100 cm³ of a solution of dichloromethane containing 54 g (0.13 mole)of the imidazolide of diisopropylidene triglycerol, prepared inaccordance with Example 1(a), there are added 19.65 g (0.106 mole) ofdodecylamine dissolved in 150 cm³ of the same solvent. The reactionmedium is stirred at ambient temperature overnight after which it iswashed three times with 100 cm³ of water. It is dried on sodium sulfateand the solvent is evaporated under reduced pressure. 62 g of a verylightly colored viscous oil are recovered.

60 g of this resulting oily product are dissolved in 300 cm³ ofmethanol. 5 cm³ of 5N HCl are then added. The reaction mixture is thenstirred at ambient temperature overnight at which point the solvent isevaporated under reduced pressure. 49.2 g of a viscous oil arerecovered.

30 g of this oil are purified on a silica column (Kieselgel 60, Merck)with, as eluant, a 90:10 mixture of dichloromethane and methanol.

12 g of a compound of formula I wherein R is dodecyl, in the form of awhite wax, are recovered.

The NMR ¹³ C spectrum is in accord with the structure indicated.

EXAMPLE 3 Compound of formula I wherein R is oleyl

To 100 cm³ of a solution of dichloromethane containing 5 g (0.12M) ofthe imidazolide of diisopropylidene triglycerol, prepared in accordancewith Example 1 (a), there are added 26.75 g (0.1M) of oleylaminedissolved in 100 cm³ of the same solvent. The reaction mixture is thenstirred for 5 hours and the solvent is then removed under reducedpressure. 76 g of an oil are recovered which is then purified by passageon a fritted glass filled with Kieselgel 60 H silica (Merck) and byeluting with a 9:1 mixture of dichloromethane and methanol.

After removal of the solvent under reduced pressure, 66 g of thecompound in the form of an oil are recovered. 60 g of this oil are thenhydrolyzed by dissolving it in 250 cm³ of ethanol in the presence of 30cm³ of 1N HCl and by heating the reaction medium 4 hours at 60° C.

After removal of the solvent under reduced pressure the resulting wax ispurified by passage on a fritted glass filled with Kieselgel 60 H silicaand with, as eluant, a 95:5 mixture of dichloromethane and methanol.

40 g of the compound of formula I wherein R is oleyl are recovered inthe form of a translucent wax.

The NMR ¹³ C spectrum is in agreement with the structure indicated.

Examples of Preparing Wax Microdispersion--Examples A-D

These wax microdispersion are prepared in accordance with the methoddescribed above. The wax employed is Carnauba wax. The emulsifying agentis a compound of formula I. The constituents and the amounts thereof, aswell as the physico-chemical characteristics of the resultingmicrodispersion (appearance, average diameter of the wax particles,polydispersivity) are set forth in the following Table:

    __________________________________________________________________________    Emulsifying agent                                                                           Additive Amount                                                                             Physico-chemical characteristics                           Amount   Amount                                                                             of wax      Average                                                                            Poly-                                 Example                                                                            R   (%).sup.(1)                                                                        Nature                                                                            (%).sup.(1)                                                                        (%).sup.(1)                                                                        Appearance                                                                           diameter                                                                           dispersivity                          __________________________________________________________________________    A    C.sub.16 H.sub.33                                                                 2.11 KOH 0.03 10   yellowish                                                                            110 nm                                                                             0.2                                                               opalescent                                                                    liquid                                            B    C.sub.12 H.sub.25                                                                 1.88 DCP.sup.(2)                                                                       0.09 10   whitish                                                                              258 nm                                                                             0.13                                                              liquid                                            C    "   "    KOH 0.03 10   whitish                                                                              208 nm                                                                             0.12                                                              slight bloom                                                                  liquid                                            D    C.sub.18 H.sub.35                                                                 2.21 KOH 0.03 10   yellowish                                                                             71 nm                                                                             0.14                                                              opalescent                                                                    liquid                                            __________________________________________________________________________     .sup.(1) weight percent relative to 100 g of dispersion in water              .sup.(2) DCP = Dicetylphosphate (sodium salt)                            

As a comparison an attempt was made to prepare a wax microdispersionunder the same conditions (emulsifying agent: 1.93%; KOH: 0.03%; wax:10%) using as the emulsifying agent a compound having the formula: C₁₆H₃₃ OCH(CH₂ OCH₂ CHOHCH₂ OH)₂. It was not possible to obtain amicrodispersion.

Examples of Preparing Cosmetic Compositions (Examples CC1-CC5)

Example CC1

The following hair care composition is prepared by incorporation in thewax microdispersion the other adjuvants in the order indicated:

    ______________________________________                                        Wax microdispersion, obtained in Example A                                                              98    g                                             Hydroxypropylmethylcellulose, sold by                                                                   1.5   g                                             Dow Chemical under the trade                                                  name "METHOCEL F4M"                                                           Methylparahydroxybenzoate 0.2   g                                             Derivative of imidazolidinyl urea,                                                                      0.3   g                                             sold under the trade name                                                     "GERMALL 115" by Sutton Labs                                                  ______________________________________                                    

This composition is applied to clean and dry hair, taking care to spreadit all along the length of the hair. 2 to 5 g of the composition areused per head of hair. The resulting hair style exhibits fullness and iscontrolled or disciplined.

Example CC2

A before shampoo composition, in the form of a fluid gel, is prepared byincorporating in the wax microdispersion the other adjuvants, in theorder indicated:

    ______________________________________                                        Wax microdispersion obtained in Example B                                                               20     g                                            Crosslinked polyacrylic acid,                                                                           1      g                                            (MW: 1,250,000), sold by Goodrich                                             under the trade name "CARBOPOL 941"                                           Derivative of imidazolidinyl urea,                                                                      0.3    g                                            sold under the trade name                                                     "GERMALL 115" by Sutton Labs                                                  Sodium hydroxide, sufficient for pH = 7                                       Water, sufficient amount for                                                                            100    g                                            ______________________________________                                    

This composition is applied with good spreading to dry but not washedhair.

After a contact time of 2 to 3 minutes the hair is rinsed with water andthen shampooed.

Soft, shiny and disciplined hair having volume or fullness is obtained.

Example CC3

A composition for the hair is prepared by incorporating in the waxmicrodispersion the other adjuvants, in the order indicated:

    ______________________________________                                        10% Carnauba wax microdispersion,                                                                    99.65 g                                                prepared according to Example C                                               Methylparahydroxybenzoate                                                                            0.15 g                                                 Derivative of imidazolidinyl urea,                                                                   0.20 g                                                 sold under the trade name                                                     "GERMALL 115" by Sutton Labs                                                  ______________________________________                                    

This composition is used in the manner set forth in Example CC1.

The hair exhibits fullness after application of this composition and isdisciplined and soft.

Example CC4

The following before-shampooing treating composition is prepared byincorporating in the wax microdispersion the other adjuvants in theorder indicated:

    ______________________________________                                        10% Carnauba wax microdispersion,                                                                     97.5 g                                                prepared in accordance with Example D                                         Hydroxypropylcellulose, sold under the                                                                2.0 g                                                 trade name "KLUCEL H" be Hercules                                             Methylparahydroxybenzoate                                                                             0.2 g                                                 Derivative of imidazolidinyl urea,                                                                    0.3 g                                                 sold under the trade name                                                     "GERMALL 115" by Sutton Labs                                                  ______________________________________                                    

The composition is applied under the conditions set forth in ExampleCC2. The hair thus treated exhibits much volume and is shiny and soft.

Example CC5

The following composition for the hair is prepared by incorporating inthe wax microdispersion the other adjuvants, in the order indicated:

    ______________________________________                                        Wax microdispersion obtained in Example C                                                                 10     g                                          "CARBOPOL 941"              1.5    g                                          NaOH                        0.6    g                                          PEG-15 COCAMINE             3      g                                          GERMALL 115                 0.2    g                                          Methylparahydroxybenzoate   0.2    g                                          Potassium sorbate           0.3    g                                          Perfume, sufficient amount                                                    Triethanolamine, sufficient amount for pH = 7                                 Water, sufficient mount for 100    g                                          PEG-15 COCAMINE: Polyethyleneglycolamine of                                   copra acid, according to the definition of                                    CTFA (Cosmetic, Toiletry and Fragrance                                        Association), sold by Akzo under the trade name                               "ETHOMEEN C25".                                                               ______________________________________                                    

This composition is applied with good spreading to dry and clean hair.After this treatment, the hair exhibits volume and is shiny anddisciplined.

We claim:
 1. In a cosmetic composition containing a surfactant or anemulsifying agent the improvement comprising as the surfactant oremulsifying agent, at least one compound of formula I

    R--NHCOOCH(CH.sub.2 OCH.sub.2 CHOHCH.sub.2 OH).sub.2       (I)

wherein R represents alkyl, optionally unsaturated, having 10 to 20carbon atoms.
 2. The cosmetic composition of claim 1 wherein R isselected from the group consisting of n-decyl, n-dodecyl, n-tetradecyl,n-hexadecyl, n-octadecenyl, n-hexyldecyl, 2-octyldodecyl and2-heptylundecyl.
 3. The cosmetic composition of claim 1 wherein saidcompound of formula I is provided in the form of a wax microdispersionin an aqueous liquid vehicle.
 4. The cosmetic composition of claim 3wherein said wax is selected from Carnauba wax, Candelilla wax, Alfa waxor mixtures thereof.
 5. The cosmetic composition of claim 3 wherein thewax/emulsifying agent weight ratio ranges from 1 to
 30. 6. The cosmeticcomposition of claim 3 wherein said emulsifying agent is present in anamount ranging from 0.01 to 25 weight percent.
 7. The cosmeticcomposition of claim 3 wherein said wax is present in an amount rangingfrom 0.1 to 40 weight percent.
 8. The cosmetic composition of claim 3wherein the wax/emulsifying weight ratio ranges from 1 to 30.